CN106701079B - A kind of near infrared region mechanoluminescence fluorescent powder and preparation method thereof - Google Patents
A kind of near infrared region mechanoluminescence fluorescent powder and preparation method thereof Download PDFInfo
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- 238000005166 mechanoluminescence Methods 0.000 title claims abstract description 45
- 239000000843 powder Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000011575 calcium Substances 0.000 claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 16
- 150000001875 compounds Chemical class 0.000 claims abstract description 11
- 238000000227 grinding Methods 0.000 claims abstract description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000012298 atmosphere Substances 0.000 claims abstract description 5
- 150000002798 neodymium compounds Chemical class 0.000 claims abstract description 5
- 230000001681 protective effect Effects 0.000 claims abstract description 5
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 5
- 239000011593 sulfur Substances 0.000 claims abstract description 5
- 150000003752 zinc compounds Chemical class 0.000 claims abstract description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 4
- 239000012856 weighed raw material Substances 0.000 claims abstract description 3
- 239000011701 zinc Substances 0.000 claims description 11
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 8
- 239000005083 Zinc sulfide Substances 0.000 claims description 8
- 239000013078 crystal Substances 0.000 claims description 8
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 claims description 8
- 230000003595 spectral effect Effects 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 5
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 4
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 4
- RCYIWFITYHZCIW-UHFFFAOYSA-N 4-methoxybut-1-yne Chemical compound COCCC#C RCYIWFITYHZCIW-UHFFFAOYSA-N 0.000 claims description 3
- MIJKIIBNAPRONL-UHFFFAOYSA-N acetic acid;neodymium Chemical compound [Nd].CC(O)=O MIJKIIBNAPRONL-UHFFFAOYSA-N 0.000 claims description 3
- 239000012300 argon atmosphere Substances 0.000 claims description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 3
- 239000000920 calcium hydroxide Substances 0.000 claims description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000292 calcium oxide Substances 0.000 claims description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 3
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 claims description 3
- CFYGEIAZMVFFDE-UHFFFAOYSA-N neodymium(3+);trinitrate Chemical compound [Nd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CFYGEIAZMVFFDE-UHFFFAOYSA-N 0.000 claims description 3
- 229940043430 calcium compound Drugs 0.000 claims 1
- 150000001674 calcium compounds Chemical class 0.000 claims 1
- 238000002329 infrared spectrum Methods 0.000 abstract 1
- 238000005303 weighing Methods 0.000 abstract 1
- 230000005284 excitation Effects 0.000 description 14
- 238000001228 spectrum Methods 0.000 description 12
- 229910052593 corundum Inorganic materials 0.000 description 11
- 239000010431 corundum Substances 0.000 description 11
- 229910052779 Neodymium Inorganic materials 0.000 description 9
- 230000007704 transition Effects 0.000 description 6
- 238000004020 luminiscence type Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
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- 238000000295 emission spectrum Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 238000000634 powder X-ray diffraction Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
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- 238000005390 triboluminescence Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
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- 238000012544 monitoring process Methods 0.000 description 2
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 2
- 238000005057 refrigeration Methods 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- 229910017488 Cu K Inorganic materials 0.000 description 1
- 229910017541 Cu-K Inorganic materials 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 102000001554 Hemoglobins Human genes 0.000 description 1
- 108010054147 Hemoglobins Proteins 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000011398 Portland cement Substances 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
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- 238000010894 electron beam technology Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000000103 photoluminescence spectrum Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- -1 rare earth ions Chemical class 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 229940083045 riax Drugs 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000000904 thermoluminescence Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7756—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing neodynium
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Luminescent Compositions (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
The invention discloses a kind of near infrared region mechanoluminescence fluorescent powder, expression general formula is Ca(1‑x)ZnOS:xNd3+, wherein 0.05%≤x≤1.0%.The invention also discloses the preparation methods of above-mentioned near infrared region mechanoluminescence fluorescent powder: (1) weighing calcium containing compound, sulfur-containing compound, zinc compound respectively by each element mol ratio and contain neodymium compound as raw material；(2) it by after the weighed raw material grinding uniformly of step (1), is roasted under protective atmosphere or vacuum；(3) sample after roasting is taken out, grinding obtains near infrared region mechanoluminescence fluorescent powder.The mechanoluminescence peak of fluorescent powder of the invention under frictional force and pressure is located at 900~1400nm near infrared spectrum, it is near-infrared luminous can also be by ultra-violet (UV) band, the yellow light of 500~550nm, orange light and 808nm laser near 600nm effectively excite.
Description
Technical field
The present invention relates to luminescent material, in particular to a kind of near infrared region mechanoluminescence fluorescent powder and preparation method thereof.
Background technique
Shining is that interior of articles absorbs the process that nonequilibrium radiation is converted into after energy in some way, and shining can be with many
Mode excites, the luminescence generated by light of for example well known ultraviolet excitation, electron-beam excitation cathode-ray luminescence, be electrically excited
Electroluminescent, the thermoluminescence of thermal excitation etc..But for mechanoluminescence, i.e., material the mechanical external force the effects of under it is luminous existing
Relatively fewer as studying, with continuous exploration in nearly more than 20 years, researchers had found and are prepared for a variety of with power cause hair
The fluorescent powder of optical property.It is directly proportional to suffered stress intensity etc. with low in cost, stable luminescent property, luminous intensity
Advantage, in detection, the fields such as stress intensity and its distribution are great application prospect.
Inorganic compound field, in many oxide, fluoride, sulfide, phosphate, silicate, aluminate, stannic acid
Mechanoluminescence phenomenon is had been found that in the matrix such as salt, nitrogen oxides, oxysulfide, Doped ions concentrate on transient metal Mn2+From
Sub and a variety of rare earth ions.But presently found mechanoluminescence wave band be but limited only to from ultraviolet light, blue and green light to
The visible light wave range of feux rouges.Near-infrared luminous mechanoluminescence fluorescent powder is not reported slowly but.Compared with visible light, near-infrared
Light has stronger penetrability, such as penetrates window (700~1000nm and 1100~1350nm) with deep well in biology
Tissue penetration is capable of the absorption of selectivity to hemoglobin, is widely used in terms of the diagnosis of disease and treatment.Near infrared light
Also there are a variety of detection abilities, be widely used in petroleum industry, agricultural and grocery trade and life science pharmacy industry etc..In addition,
Mechanoluminescence fluorescent powder can be used as the structural safety monitoring field that a kind of stress detection device is used for building, real time reaction building
The stress intensity and its distribution that object or certain mechanical parts are subject in the operating condition.It is compared to visible light, near infrared light pair
Portland cement and aluminate cement have permeability well, can further monitor the stress distribution of interior of building even
The spread scenarios of micro-crack.Therefore, developing near infrared region there is the fluorescent powder of mechanoluminescence will expand mechanoluminescence material significantly
Expect the application in other field.
Summary of the invention
In order to overcome luminous the shortcomings that being limited only to visible waveband of mechanoluminescence fluorescent powder of the prior art and insufficient,
The purpose of the present invention is to provide a kind of near infrared region mechanoluminescence fluorescent powder, mechanoluminescence peak is located at 900~1400nm spectrum
Area, light emitting main peak are respectively 910nm, 1094nm and 1390nm.
The purpose of the present invention is achieved through the following technical solutions:
A kind of near infrared region mechanoluminescence fluorescent powder, expression general formula are Ca(1-x)ZnOS:xNd3+, wherein 0.05%≤x≤
1.0%.
The near infrared region mechanoluminescence fluorescent powder, crystal structure belong to hexagonal crystal system, light emitting ionic Nd3+Ion.
The near infrared region mechanoluminescence fluorescent powder, mechanoluminescence peak are located at 900~1400nm spectral regions, light emitting main peak
Respectively 910nm, 1094nm and 1390nm.
A kind of preparation method of near infrared region mechanoluminescence fluorescent powder, comprising the following steps:
(1) each element mol ratio Ca:Zn:S:Nd=1-x:1:1:x is pressed, wherein 0.05%≤x≤1.0%；Claim respectively
It takes calcium containing compound, sulfur-containing compound, zinc compound and contains neodymium compound as raw material；
(2) it by after the weighed raw material grinding uniformly of step (1), is roasted under protective atmosphere or vacuum, temperature 1000
~1200 DEG C, the time is 2~10 hours；
(3) sample after roasting in step (2) is taken out, grinding obtains near infrared region mechanoluminescence fluorescent powder.
Step (1) protective atmosphere is argon atmosphere or nitrogen atmosphere.
Step (1) calcium containing compound is calcium carbonate, calcium oxide, any one in calcium hydroxide.
The sulfur-containing compound is zinc sulphide.
The zinc compound is zinc sulphide.
It is described containing neodymium compound be neodymia, neodymium nitrate, acetic acid neodymium and neodymium hydroxide in any one.
Compared with prior art, the present invention has the following advantages and beneficial effects:
(1) near infrared region mechanoluminescence fluorescent powder of the invention, mechanoluminescence peak are located at 900~1400nm spectral regions, hair
Light main peak is respectively 910nm, 1094nm and 1390nm.
(2) near infrared region mechanoluminescence fluorescent powder of the invention it is near-infrared luminous can also by ultra-violet (UV) band, 500~
The yellow light of 550nm, orange light and 808nm laser near 600nm effectively excite, characteristic spectral emission and mechanoluminescence spectrum one
It causes.
(3) near infrared region mechanoluminescence fluorescent powder of the invention has under the mechanical forces such as frictional force, pressure, impact force
Apparent near-infrared luminous phenomenon, luminous intensity and stress intensity are in good linear relationship.
(4) near infrared region mechanoluminescence fluorescent powder of the invention is burnt into using one-step method, low in cost, preparation process is simple
Single, preparation process is not related to the substance being harmful to the human body, and is convenient for volume production.
Detailed description of the invention
Fig. 1 is powder x-ray diffraction spectrum of the different levels of doping sample under 1100 DEG C of roastings in embodiment 1.
Fig. 2 is emission spectrum of the different levels of doping sample under 808nm laser excitation in embodiment 1.
Fig. 3 is the luminous intensity under 808nm laser excitation in embodiment 1 with doping concentration variation relation.
Fig. 4 is CaZnOS:0.5%Nd in embodiment 13+The emission spectrum of sample.
Fig. 5 is CaZnOS:0.5%Nd in embodiment 13+The excitation spectrum of sample.
Fig. 6 is the tribo-luminescence spectrum of sample in embodiment 2.
Fig. 7 is mechanoluminescence spectrum of the sample under different size pressure in embodiment 3.
Fig. 8 is the mechanoluminescence integrated intensity of sample and the matched curve of pressure size relationship in embodiment 3.
Specific embodiment
Below with reference to embodiment, the present invention is described in further detail, embodiments of the present invention are not limited thereto.
Embodiment 1
Calcium carbonate, zinc sulphide, neodymia are chosen as raw material, by each element mol ratio Ca:Zn:S:Nd=1-x:1:1:
X weighs three kinds of raw materials of compound respectively, totally five groups, matches as follows:
(1) Ca:Zn:S:Nd=0.999:1:1:0.001, corresponding x=0.10%；
(2) Ca:Zn:S:Nd=0.998:1:1:0.002, corresponding x=0.20%；
(3) Ca:Zn:S:Nd=0.997:1:1:0.003, corresponding x=0.30%；
(4) Ca:Zn:S:Nd=0.995:1:1:0.005, corresponding x=0.50%；
(5) Ca:Zn:S:Nd=0.990:1:1:0.010, corresponding x=1.00%；
Controlling mixture total weight is 5g, and 5g mixed raw material is ground uniformly, is put into corundum crucible, then crucible is placed in
In corundum boat, corundum boat is pushed into tube furnace, roasts 3 hours under nitrogen atmosphere in 1100 DEG C, with furnace natural cooling, can obtain
One doping concentration gradient series near-infrared mechanoluminescence fluorescent powder Ca1-xZnOS:xNd3+。
Fig. 1 is the powder x-ray diffraction spectrum that different levels of doping sample roasts 3 hours in 1100 DEG C in the present embodiment, spectrum
Line is measured using Japan's Rigaku D/max-IIIA X-ray diffractometer, test voltage 40kV, scanning speed 1.2o/ min is surveyed
Electric current 40mA is tried, Cu-K α 1X ray is selected, wavelength isX-ray diffraction analysis shows to roast 3 at 1100 DEG C
Hour available CaZnOS pure phase, belongs to hexagonal crystal system, and the doping of neodymium does not have an impact the synthesis of crystal phase, and is not observed
Neodymium and its compound phase.
Fig. 2 is launching light spectrogram of the different levels of doping sample under 808nm laser excitation in the present embodiment, is used
The measurement of 320 type spectrometer of Jobin-Yvon company's T riax, laser power are 0.8 watt, and the data acquired integrated time is 0.2
Second, scanning step 1nm.Under 808nm laser excitation, Nd3+4f electronics from ground state 4I9/2Transit to excitation state 4F5/2, sample
Emission spectrum is that linear emission peak is located within the scope of 900~1400nm, and wherein 910nm and 938nm emission peak belong to 4F3/2It arrives
4I9/2Energy level transition；1094nm and 1135nm emission peak belong to 4F3/2To 4I11/2Energy level transition；1390nm emission peak belongs to
4F3/2To 4I13/2Energy level transition.
As shown in figure 3, under 808nm laser excitation, with Nd3+Ion concentration increases the variation of luminous intensity, mole dense
Spend Nd3+It shines when=0.50% most strong, continues growing Nd3+Ion concentration, generation concentration Quenching.
Fig. 4 is sample CaZnOS:0.5%Nd in the present embodiment3+Photoluminescence spectra under 290nm and 600nm excitation
Figure is measured using 920 stable state of Edinburgh, Britain FLS and transient luminescence spectrometer, and xenon lamp power is 450 watts, and detector is Japan
Hamamatsu refrigeration mode R928P photomultiplier tube (- 1250 volt of operating voltage), data acquired integrated time are 0.2 second, scanning
Step-length is 1nm.Sample is that linear emission peak is located within the scope of 900~1400nm under 290nm and 600nm excitation, wherein 910nm
4F is belonged to 938nm emission peak3/2To 4I9/2Energy level transition；1094nm and 1135nm emission peak belong to 4F3/2To 4I11/2Energy
Order transition；1390nm emission peak belongs to 4F3/2To 4I13/2Energy level transition.And by Fig. 5,600nm is red, and light activated efficiency is obvious
Better than the excitation of ultraviolet light.Fig. 5 is sample CaZnOS:0.5%Nd in the present embodiment3+Excitation spectrum.Corresponding monitoring wavelength
Respectively 910nm and 1094nm；It is measured using 920 stable state of Edinburgh, Britain FLS and transient luminescence spectrometer, xenon lamp power is
450 watts, detector is Japan Hamamatsu refrigeration mode R928P photomultiplier tube (operating voltage: 1250 volts), data acquisition product
It is 0.2 second between timesharing, scanning step 1nm.As shown in figure 3, sample can also be by 500 other than the excitation peak in ultra-violet (UV) band
The yellow light of~550nm and the orange light near 600nm effectively excite, and the result is consistent with transmitting spectral property.
Embodiment 2
Calcium oxide, zinc sulphide and neodymium nitrate are chosen as raw material, according to molar ratio Ca:Zn:S:Nd=0.995:1:1:
0.005 weighs a certain amount of above-mentioned raw materials respectively, after the ground mixing of raw material, takes a part that PVA is added and is granulated, 5g is taken to make
Raw material after grain carries out tabletting, and semi-automatic tablet press machine is taken to keep 2min under 10Mpa, and the cylinder for obtaining 25 × 10mm is thin
Piece.Thin slice is placed in corundum boat, is roasted 4 hours under 1100 DEG C of vacuum atmospheres；Powder x-ray diffraction is analysis shows it is
CaZnOS crystal phase.
By the CaZnOS:0.5%Nd after roasting3+Sample is fixed on sample stage, using the corundum rod for having sharp tip
It rubs, while luminous signal of the sample under frictional force excitation is collected using spectrometer.Friction tips and optical fiber are kept to visit
Head distance is 8mm.When carrying out tribo-luminescence experiment in darkroom, human eye can only observe weaker luminous signal.Fig. 6 is shown as
The tribo-luminescence spectrum of sample, in 900~1400 near-infrared region spectrum, there are three transmitting main peaks to be located at 910nm,
1094nm and 1390nm, it is consistent with the transmitting peak position of the luminescence generated by light of Fig. 3 sample.
Embodiment 3
Calcium hydroxide, zinc sulphide, neodymium hydroxide are chosen as raw material, according to molar ratio Ca:Zn:S:Nd=0.995:1:1:
0.005, weigh a certain amount of above-mentioned raw materials.After the ground mixing of raw material, take in right amount in corundum crucible, then crucible is placed in corundum
In boat, corundum boat is pushed into tube furnace, is roasted 8 hours under argon atmosphere in 1000 DEG C, with furnace natural cooling, by gained sample
Grinding can uniformly obtain near infrared region mechanoluminescence fluorescent powder CaZnOS:0.5%Nd3+.By gained fluorescent powder and transparent epoxy tree
Rouge is uniformly mixed with the mass ratio of 5:1, is solidified 8h at room temperature and is obtained cylindric fluorescent powder resin composite materials, having a size of 25 ×
15mm.Using WEW-600 type microcomputer control universal testing machine carry out pressure luminous test, control apply pressure limit be 0N~
5000N, while pressure luminescent spectrum is collected using spectrometer.
Fig. 7 is luminescent spectrum figure of the fluorescent powder resin composite materials under different size pressure, as seen from the figure luminous intensity
Enhance with the increase of pressure applied, but three transmitting main peak peak positions are kept at 910nm, 1094nm, 1390nm does not have
Variation.By Fig. 8, luminescent spectrum integrated intensity and pressure applied size under different pressures carry out linear fit, the goodness of fit
R2=0.9883, show that good linear relationship is presented in the two.
Embodiment 4
Calcium carbonate, zinc sulphide, acetic acid neodymium are chosen as raw material, according to each element molar ratio Ca:Zn:S:Nd=0.995:1:
1:0.005 corresponding x=0.5%；Three kinds of raw materials are weighed respectively, and control mixture total weight is 5g.After the ground mixing of raw material, put
Enter in corundum crucible, then crucible is placed in corundum boat, corundum boat is pushed into tube furnace, is roasted under nitrogen atmosphere in 1200 DEG C
3 hours, with furnace natural cooling, near infrared region mechanoluminescence fluorescent powder CaZnOS:0.5%Nd can be obtained3+, X-ray diffraction analysis
Show it for CaZnOS crystal phase.The spectral property of fluorescent powder is similar in embodiment 1.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by the embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (9)
1. a kind of near infrared region mechanoluminescence fluorescent powder, which is characterized in that expression general formula is Ca(1-x)ZnOS:xNd3+, wherein
0.05%≤x≤1.0%.
2. mechanoluminescence fluorescent powder near infrared region according to claim 1, which is characterized in that crystal structure belongs to hexagonal crystal
System, light emitting ionic Nd3+Ion.
3. mechanoluminescence fluorescent powder near infrared region according to claim 1, which is characterized in that mechanoluminescence peak is located at 900
~1400nm spectral regions, light emitting main peak are respectively 910nm, 1094nm and 1390nm.
4. a kind of preparation method of near infrared region mechanoluminescence fluorescent powder, which comprises the following steps:
(1) each element mol ratio Ca:Zn:S:Nd=1-x:1:1:x is pressed, wherein 0.05%≤x≤1.0%；It weighs and contains respectively
Calcium compound, sulfur-containing compound, zinc compound and containing neodymium compound as raw material；
(2) it by after step (1) weighed raw material grinding uniformly, being roasted under protective atmosphere or vacuum, temperature is 1000~
1200 DEG C, the time is 2~10 hours；
(3) sample after roasting in step (2) is taken out, grinding obtains near infrared region mechanoluminescence fluorescent powder.
5. the preparation method of mechanoluminescence fluorescent powder near infrared region according to claim 4, which is characterized in that step (1)
The protective atmosphere is argon atmosphere or nitrogen atmosphere.
6. the preparation method of mechanoluminescence fluorescent powder near infrared region according to claim 4, which is characterized in that step (1)
The calcium containing compound is calcium carbonate, calcium oxide, any one in calcium hydroxide.
7. the preparation method of mechanoluminescence fluorescent powder near infrared region according to claim 4, which is characterized in that the sulfur-bearing
Compound is zinc sulphide.
8. the preparation method of mechanoluminescence fluorescent powder near infrared region according to claim 4, which is characterized in that described to contain zinc
Compound is zinc sulphide.
9. the preparation method of mechanoluminescence fluorescent powder near infrared region according to claim 4, which is characterized in that described to contain neodymium
Compound is any one in neodymia, neodymium nitrate, acetic acid neodymium and neodymium hydroxide.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710053820.0A CN106701079B (en) | 2017-01-22 | 2017-01-22 | A kind of near infrared region mechanoluminescence fluorescent powder and preparation method thereof |
| PCT/CN2017/113140 WO2018133543A1 (en) | 2017-01-22 | 2017-11-27 | Near-infrared mechanoluminescence fluorescent powder and preparation method therefor |
Applications Claiming Priority (1)
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| CN107739211B (en) * | 2017-11-02 | 2020-08-04 | 赣州中蓝稀土新材料科技有限公司 | Yellow-green mechanoluminescence ceramic material and preparation method thereof |
| CN108753285A (en) * | 2018-04-28 | 2018-11-06 | 华南理工大学 | A kind of near-infrared mechanoluminescence stannate and its preparation method and application |
| CN113372913B (en) * | 2021-06-09 | 2023-03-21 | 中国科学院兰州化学物理研究所 | Stress luminescent elastomer and preparation method and application thereof |
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| CN105400511A (en) * | 2015-09-15 | 2016-03-16 | 青岛大学 | Multifunctional luminescent material with adjustable light color and high brightness as well as application thereof |
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| CN102329612B (en) * | 2011-06-10 | 2014-04-02 | 中国科学院上海硅酸盐研究所 | High-luminance stress luminescent material with laminar crystal structure as well as preparation method and application thereof |
| CN106701079B (en) * | 2017-01-22 | 2019-06-18 | 华南理工大学 | A kind of near infrared region mechanoluminescence fluorescent powder and preparation method thereof |
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| CN105400511A (en) * | 2015-09-15 | 2016-03-16 | 青岛大学 | Multifunctional luminescent material with adjustable light color and high brightness as well as application thereof |
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